CN1048553A - Contain poly-(aromatic substance that alkenyl replaces) and elastomeric polymer composition and preparation method thereof - Google Patents

Contain poly-(aromatic substance that alkenyl replaces) and elastomeric polymer composition and preparation method thereof Download PDF

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CN1048553A
CN1048553A CN90104498A CN90104498A CN1048553A CN 1048553 A CN1048553 A CN 1048553A CN 90104498 A CN90104498 A CN 90104498A CN 90104498 A CN90104498 A CN 90104498A CN 1048553 A CN1048553 A CN 1048553A
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CN1026238C (en
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劳里吐斯·尼高拉思·伊达·哈伯塔思·尼里森
格拉达思·约翰·马里·考宁
约翰·马里·兹得维尔特
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/905—Polyphenylene oxide

Abstract

The present invention relates to contain poly-(aromatic substance that alkenyl replaces) and elastomeric polymer composition, it is obtained by following method: (a) with acyl halide, acid anhydrides or ketenes the polyphenylene oxide polymkeric substance close with structure transformed in the aromatic monomer that at least a alkenyl replaces; (b) at least a EPDM rubber of dissolving and alternative partially hydrogenated Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock A-B; (c) mixture that obtains being carried out pre-polymerization is that 5 to 20% (d) are suspended in the thing piece that prepolymerization gets in the water-bearing media up to the polymerization degree; (e) adopt thermal initiation and radical to cause and carry out polymerization, polymerization is selectively carried out in whipping agent.The invention still further relates to the preparation method of this polymer composition.

Description

Contain poly-(aromatic substance that alkenyl replaces) and elastomeric polymer composition and preparation method thereof
The present invention relates to contain poly-(aromatic substance that alkenyl replaces) and elastomeric polymer composition, more particularly, relate to and contain polyphenyl ethers or close polymkeric substance, poly-(aromatic substance that alkenyl replaces) and the elastomeric polymer composition of structure, with and preparation method thereof.
For the mechanical property of improving polyphenylene oxide resin and gathering the composition of (alkenyl aromatic compounds) resin, the past has proposed the method for compositions that many preparations contain polyphenylene oxide resin, elastomerics and poly-(aromatic substance that alkenyl replaces) resin.
For example, United States Patent (USP) № .3,664,977 disclose the resin that a kind of shock strength is improved, its preparation method comprises: under 70-170 ℃ temperature, make the mixture to contain alkenyl aromatic compounds (78-85 part (weight)) and to contain a kind of rubber material (30 to 10 parts (weight)) carry out hot mass polymerization continuously, above-mentioned rubber material preferably is selected from cr, butadiene-styrene copolymer rubber, butadiene acrylonitrile copolymer rubber, polyisoprene rubber, polybutadiene rubber and ethylene propylene rubber; Then after forming, the dispersion one from rubbery polymer begins to reach 40% (weight) during this, adding 40 to 20% ((weight) (gross weight with final polymkeric substance is a benchmark) polyphenylene oxide in the polymeric blends to the polymkeric substance total concn; Then fully stir and 70-170 ℃ temperature under resulting mixture is proceeded mass polymerization, to finish polyreaction.
From for example German Patent № .2,342, in 119, people learn, a kind of high-heat plastic composition, it comprises: (a) a kind of polyphenylene oxide resin, its content is preferably 20 to 80% (weight) of composition, (b) a kind of polystyrene resin of modified rubber, the polystyrene of wherein said modified rubber is represented a kind of polystyrene substrate, wherein by the discontinuous phase that is encapsulated in the styrene homopolymers granulometric composition in elastoprene film regular-scattered, and above-mentioned particulate mean size is about 01 to 07 μ m, thereby make the thickness of film not exceed 1/4th of average particulate diameter, the content of above-mentioned elastoprene is 1 to 10% (weight) of the polystyrene of modified rubber, is 3 to 8% (weight) preferably.
Afterwards, United States Patent (USP) № .4 for example, 118,348 disclose preparation contains rubber, the special methods of the composition of polyphenylene oxide resin and alkenyl aromatic addition polymer, this method comprises: use alkenyl aromatic monomer as phenol and the used solvent of polyphenylene oxide resin oxidative coupling; Add rubber and polyblend then, to form the blend of rubber, alkenyl aromatic addition polymer and polyphenylene oxide resin.The content of rubber components can be 1 to 25 part (weight), and the content of alkenyl aromatic addition polymer can be 5 to 95 parts (weight), and the content of polyphenylene oxide resin can be 10 to 90 parts (weight).
United States Patent (USP) № 4,148,843 disclose a kind of preparation contains (a) and (method for compositions of (b), wherein (a) is for being selected from the end capped polyhydroxyether resin of compound of carboxylic acid halides, acid anhydrides and ketenes, (b) be the alkenyl aromatic polymer resin, this method comprises: form the mixture of end capped polyphenylene oxides in alkenyl aromatic monomer, then at high temperature heat described mixture time enough, to form described composition.Though this patent is capable the pointing out of the 3rd hurdle 35-47, various rubber impact modifiers can join in the composition in principle, but the final composition of not pointing out how to obtain to have the feature that satisfies modern project plastics institute requirement for these professional those of skill in the art.
From for example English Patent № .1,494,759, people have also known a kind of method for preparing polymkeric substance, the existence that it is included in the rubber of ethylene/propene/the 3rd component goes on foot body suspension polymerization alkenyl aromatic compounds by two down, and the first step of this method is included under the oxygen existence and carries out mass polymerization under the pressure of 005 to 10 normal atmosphere (gauge pressure).More particularly, used rubber is can be by by 70 to 30% (weight) ethene, and 30 to 70% (weight) propylene and 05 to 15% (weight) (gross weight with ethene and propylene is a benchmark) obtain as the polymerization of the diene of the 3rd component.The example of described diene has 5-vinyl norbornene, Dicyclopentadiene (DCPD), 2,2,1-bicycloheptadiene and 1, the 4-hexadiene, total amount with vinyl aromatic compounds and rubber components is a benchmark, and the consumption of rubber components is preferably 1 to 20% (weight), more is preferably 4 to 15% (weight).
For example. English Patent № .1,514,408 disclose a kind of to the improving one's methods of last method, second step that it points out a method should mainly be included in a class very special percarboxylate (preferably by a kind of chloro-formic ester and a kind of hydroperoxide generate on the spot percarboxylate) have the suspension polymerization of being carried out down.
From for example european patent application № .0095098, people know, thermoplasticity thing piece based on styrene polymer modification, high impact-resistant and polyphenylene oxide also contains component (a) and mixture (b), wherein: (a) be the AB type, ABA ' type of 90-10 part (weight) and/or (AB) nThe high-elastic segmented copolymer of-X type, wherein A and A ' they are polymeric vinyl-arene block, and B is hydrogenant and/or unhydrided polymeric conjugation block, and X is the residue of multifunctional coupling agent, and n is for being 3 integer at least; (b) 10-90 part (weight) density d=0910-0945 (g/cm 3) ethylene copolymer, this multipolymer is by b1) 80-99% (weight) ethene and b2) the 1-alkene of 1-20% (weight) with at least 4 carbon atoms forms.
This european patent application points out that clearly the preparation of polymer blend is to adopt mechanical mixing, for example uses extrusion machine, and the two-phase structure particles is distributed in the matrix.
With reference to described result, the table in 17 pages especially, the those of skill in the art that responsible manufacturing has the polymer blend of the improvement characteristic that can satisfy present requirement can not tend to concentrate research to contain the composition of ethylene/propene copolymer more certainly.
From for example european patent application № .0009638, people have known a kind of method of making alkenyl aromatic homopolymers or multipolymer, this method is by making the mixture of alkenyl aromatic compounds or alkenyl aromatic compounds carry out mass polymerization continuously with thermal initiation method or the free agent of use, above-mentioned polyreaction optionally nitrile, acrylate or methacrylic ester and/or natural or elastomeric in the presence of carry out, process comprises a step, two steps or the continuous prepolymerization of multistep and a step thereafter, two steps or the continuous main polymerization of multistep and final processing.In main polymerization procedure, carry out heat exchange and even quiet mixing to polyblend.This method is particularly suitable for cinnamic homopolymerization and copolymerization, the especially copolymerization of alpha-methyl styrene, and these polyreactions are optionally carried out in the presence of EPDM (ethylene-propylene-5-ethylidene-norbornylene-2) rubber.
For example, to disclose a kind of compression set as rubber be 65% or littler (JISK6301 to european patent application № .0209874; 100 ℃ X22 hour, compression factor 25%) hydrogenated block copolymer compositions.It comprises (a) 100 parts of (weight) hydrogenated block copolymers, and this multipolymer is to obtain by the segmented copolymer that hydrogenation comprises at least two polymer blocks A (mainly being made up of vinyl substituted aromatic) and at least one polymer blocks B (mainly being made up of conjugated diolefine); (b) polyphenylene oxide resin of 11 to 233 (weight) part homopolymerization and/or copolymerization, this resin that records under 30 ℃ is 015 to 070 30 ℃ of reduced viscositys that rise chloroformic solution in 05 Grams Per Minute; (c) 10 to 500 parts (weight) is 100 to 500 parts of (weight) softener of rubber and (d) 5 to 150 parts of (weight) polyolefin resines and/or polystyrene resins preferably.These compositions can pass through conventional compounding technique, use fusing kneading machine (for example single-screw extrusion machine, twin-screw extruder, Banbury mixer, heated roll etc.) to make.
From for example european patent application № .297,633, people have known a kind of polymeric blends that comprises polyphenylene ether, polymeric amide and a kind of shock strength improving agent, above-mentioned shock strength improving agent comprises the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the partially hydrogenated diene-vinyl aromatic compounds of (a) 10-90 part (weight), and (b) 90-10 part (weight) has the segmented copolymer of the partially hydrogenated diene-vinyl aromatic compounds of at least three blocks.Polymeric blends optionally contains weighting agent in addition, fortifying fibre, fire retardant, and stablizer, dyestuff and/or pigment also optionally contain the reagent that improves the miscibility between polyphenylene oxide and the polymeric amide.
From Japanese patent application № s.63,289,060; 63,289,061; 63,256,650 and 63,251,457 can be clear that, in order to reach present desired thermal characteristics, mechanical property and combustibility, the emphasis of research and development mainly is the application facet of the modified block copolymer of polyalkenyl aromatic substance (polystyrene) and conjugated diolefine at present, promptly, optionally further transform by the hydrogenant method with by make the method for the carboxylic acid residues or derivatives thereof bonding in the unit that the carboxylic acid residues or derivatives thereof is arranged in the composition of poly-(aromatic substance that the alkenyl replaces) resin that contains polyphenylene oxide resin and modified rubber.
From these Japanese patent applications, can see, use the satisfied final composition of suitable mass expensive modified block copolymer availability.
From for example european patent application № .0,298,365, people have known an analog thermoplastic composition, it comprises following main ingredient; (a) polymeric amide of 5 to 94% (weight); (b) polyphenylene ether of 5 to 94% (weight); (c) the partially hydrogenated PQP ' of 1 to 20% (weight)-segmented copolymer, wherein, α) block P and P ' are obtained by the vinyl substituted aromatic monomer, the total content of these blocks is 25 to 40% (weight) of segmented copolymer amount, β) number-average molecular weight of block P is at most 8000 and less than the number-average molecular weight of block P ', γ) block Q is obtained by conjugate diene monomer, and its total content is 60 to 75% and δ of segmented copolymer amount) in block Q, also have two keys of 5 to 30% (weight) not to be hydrogenated; (d) vinylaromatic polymer of 1 to 50% (weight).
For example european patent application № .0300178 discloses a kind of polymeric blends, and it comprises: (a) 10-90% (weight) polyphenylene oxide; (b) 10-90% (weight) Fluorine containing olefine homopolymer or multipolymer, the weight percent of A and B adds the total weight of B with A; (c) 1-80 part (weight) vinyl aromatic compounds-(methyl) alkyl acrylate copolymer; (d) the optionally partially hydrogenated segmented copolymer of 1-20 part (weight), this multipolymer contain one or more block and one or more blocks that is obtained by the vinyl aromatic compounds unit of being obtained by conjugate unit; (e) styrene polymer of 0-200 part (weight) styrene homopolymers and/or modified rubber and (f) conventional additives of 0-50 part (weight), the parts by weight of O, D and E are 100 calculating with the parts by weight of A and B.
Although people are proceeding deep research and development, can produce attractive economically method with required thermal characteristics, mechanical property and flammable polymer composition but still press for.
Therefore, the purpose of this invention is to provide to have and improve performance and contain the polymer composition of poly-(aromatic substance of vinyl substituted) and attractive economically these composition manufacturing method of acquisition are provided.
Because the result of further investigation and exploitation is surprised to find that, available following method obtains this required polymer composition that contains poly-(aromatic substance that alkenyl replaces), and this method comprises:
(a) in the aromatic monomer that at least a alkenyl replaces, polyphenylene oxide shown in the following formula or the close polymkeric substance of structure are transformed with acyl halide, acid anhydrides or ketenes,
Figure B901044989D0000151
R in the formula 1And R 4Can respectively be hydrogen, halogen, phenyl, alkenyl, alkadienyl, aryloxy, perhaps R in the formula 1And R 4Can respectively be alkyl or alkoxyl group; these two kinds of groups can respectively contain 12 or carbon atom still less and optionally each by halogen, cyano group, hydroxyl, phenyl or amino the replacement; the alkyl or the alkoxyl group that are connected on the terminated phenol ring then can be replaced by amino, dialkyl amido or two (alkyloyl) amido; alkyl in these substituting groups respectively contains 4 or carbon atom still less, R in the formula 2And R 3Can respectively be hydrogen, halogen, phenyl, alkenyl, alkadienyl, aryloxy, perhaps R in the formula 2And R 3, as R 1And R 4Defined can respectively be uncle or secondary alkyl or uncle or secondary alkoxyl group like that, and these groups are optionally replaced R in the formula by halogen, cyano group, hydroxyl, phenyl 1, R 2, R 3And R 4In a multiple unit, can respectively be similar and different group, n is at least 50 revolution, is preferably 100 to 500, in the gross weight of final composition, the consumption of the polymkeric substance that polyphenylene oxide or structure are close is 5 to 30% (weight), is preferably 10 to 25% (weight);
(b) dissolving 5 to 20% (weight), at least a ethylene-propylene-diene monomers (EPDM) rubber of best 7 to 15% (weight) and the alternative partially hydrogenated Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock A-B of 1 to 5% (weight), optionally be mixed with a small amount of triblock copolymer A-B-A in this Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, above-mentioned weight percent is all in the gross weight of final composition; The proportion of above-mentioned rubber is 085 to 095, and mooney viscosity (125 ℃ of ML (1+4)) is 30 to 80, and therein ethylene content is 50 to 70% (weight); In above-mentioned segmented copolymer, A is poly-(alkenyl aromatic compounds) block, and B is alternative partially hydrogenated polymerized conjugated diene block, and the number-average molecular weight of segmented copolymer is 10,000 to 1,000,000, and second-order transition temperature is-20 ℃ or lower;
(c) mixture that prepolymerization obtained is 5 to 20% until the polymerization degree, is preferably 8 to 15%;
(d) the thing piece that prepolymerization is got is suspended in the water medium;
(e) adopt thermal initiation or carry out polymerization with the mode that at least a free-radical initiator causes, this polyreaction is optionally carried out in whipping agent.
The conversion of step (a) can be carried out in the aromatic monomer of one or more vinyl substituted, described monomer is selected from vinylbenzene, alpha-methyl styrene, 2, the 4-dichlorostyrene, to methoxy styrene, p-nitrophenyl ethene, p-methylstyrene, 3, the 4-dimethyl styrene, between t-butyl styrene, to dodecyl vinylbenzene, to styryl phenyl, to phenetole ethene, Vinylstyrene, p-aminophenyl ethene, right-(chloromethyl) vinylbenzene, between cyano-styrene, o-hydroxy ethene, to vinyl benzoic acid, α-propylstyrene, 3,5-diethylbenzene ethene, 2,4,6-Three methyl Benzene ethene, 4-p-methylphenyl vinylbenzene, 3,5-diphenyl benzene ethene, 3-ethyl-vinyl naphthalene, α-undecyl vinylbenzene, adjacent methyl-alpha-methyl styrene, between-methyl-alpha-methyl styrene, to methyl-alpha-methyl styrene, to methoxyl group-alpha-methyl styrene, to cyano group-alpha-methyl styrene, between-the bromo-alpha-methyl styrene, right-chloro-alpha-methyl styrene phenyl-1-vinyl naphthalene and 1,1-diphenylethlene or its mixture, wherein vinylbenzene or mainly contain the mixture of styrene monomer preferably.
Better conversion is reflected in the vinylbenzene that alternative is mixed with alpha-methyl styrene carries out.
The exemplary of the used end-capping reagent of step (a) is disclosed in the following document: european patent application № s.0,261,574 and 0,264,623, United States Patent (USP) № s.4,048,143; 4,189,417; 4,156,773 and 4,156,422.
According to a preferred embodiment of step (a), transform in the presence of catalyzer, also optionally in the presence of neutralizing agent, employing chloride of acid or non-annularity acid anhydrides carry out as end-capping reagent, and described end-capping reagent is selected from the compound of following general formula,
X in the formula 1For halogen or contain the alkyl of the individual carbon atom in 1 to 4 (best 1 to 2), this alkyl is optionally replaced by halogen, x in the formula 2Be halogen, R 5And R 6Can respectively be alkyl, alkenyl, aryl (preferably phenyl) or aralkyl (preferably aromatic yl elementary alkyl), these groups contain 1 to 12 carbon atom and are optionally contained the alkyl of 1 to 4 carbon atom or the carboxyl substituted of free or esterification by hydroxyl halogen (preferably bromine), and above-mentioned catalyzer has following general formula:
In the formula, R 9And R 10Usually be non-electron-withdrawing group, as contain the alkyl of 1 to 4 carbon atom, this alkyl is optionally by phenyl replacement at the most, R 7And R 8Be hydrogen, halogen or low alkyl group, and at same intramolecular R 9And R 10Can be similar and different.
Preferred end-capping reagent is the phenyl sulfonyl halogen compound of para-orientation when being selected from general formula I I a, x in the formula 1Be bromine or the methyl or the ethyl that are replaced by bromine, x 2Represent bromine or chlorine, wherein preferably to the 2-bromomethylphenyl sulfuryl bromide or to the 2-bromomethylphenyl SULPHURYL CHLORIDE, perhaps R among the general formula I I b 5And R 6Be the compound of identical group, wherein R 5And R 6The compound that is diacetyl oxide, benzoyl oxide and bromoacetic acid acid anhydride is preferably, preferably diacetyl oxide.
Preferred catalyzer is the following compound in the general formula III: R in the formula 9And R 10Be methyl or ethyl, and R 7And R 8Be preferably hydrogen, chlorine or methyl, preferably use N, N-dimethyl-4-aminopyridine (DMAP) is as catalyzer.
Used acid acceptor can be any basic cpd that can fully be dissolved in the reaction medium in principle.More particularly, the example of available organic bases is N, N '-two (tertiary butyl)-quadrol, N, N '-dimethyl butylamine, Di-n-Butyl Amine, triethylamine, diethylamine, picoline, quinoline, pyridine, pyrimidine, quinoxaline, Tri-n-Propylamine, tri-isopropyl amine, dimethyl Isopropylamine etc., wherein preferably triethylamine or Tri-n-Propylamine.
Acid neutralizing agent just just uses when adopting acyl halide to make end-capping reagent usually.
Another preferred embodiment according to step (a), conversion better is in the presence of metal hydride in the presence of non-nucleophilic base, is more preferably in the presence of sodium hydride or potassium hydride KH, carry out as end-capping reagent with cyclic acid anhydride, described cyclic acid anhydride is selected from the cyclic acid anhydride shown in the following general formula:
Y is the divalent group of following formula in the formula:
Figure B901044989D0000192
M is 2 to 8 integer in the formula, is 2 to 4 integer preferably, R 11And R 12Can be respectively for containing the alkyl phenyl or the aralkyl (preferably phenmethyl) of 1 to 4 carbon atom, perhaps R 11And R 12Carbon atom with carbon-to-carbon double bond forms cycloalkenyl group, cycloalkadienyl or aryl (preferably phenyl).
Preferable methods is that maleic anhydride and sodium hydride are used in combination.
As can be seen.Be characterised in that chemical fusion by the composition that the inventive method obtained, the continuous microstructure that this fusion produces has caused the improvement of mechanical property and thermal characteristics.
It is poly--2 that the exemplary of the polymkeric substance that the polyphenylene oxide of the applied general formula I of the inventive method and structure are close comprises, 6-dimethyl-1,4-phenylate (PPE); Gather-2,
6-diethyl-1, the 4-phenylate; Gather-2,6-dipropyl-1,4-phenylate;
Poly--2-methyl-6-allyl group-1, the 4-phenylate; Poly--two-tertiary butyl-dimethoxy-1, the 4-phenylate; Gather-2,6-dichloromethyl-1,4-phenylate; Poly---2,6-dibromo methyl isophthalic acid, 4-phenylate; Gather-2,6-two (chloroethyl)-1,4-phenylate; Gather-2,6-xylyl-1,4-phenylate; Gather-2,6-two chloro-1,4-phenylate; Gather-2,6-phenylbenzene-1,4-phenylate and poly--2,5 dimethyl-1, the 4-phenylate, its terminal phenol ring can have aminoalkyl group or two (alkyl) aminoalkyl group at the ortho position.
R in general formula I 1, R 2, R 3And R 4Be preferably hydrogen or contain the alkyl that the alternative of 1 to 4 carbon atom replaces, more particularly, work as R 1And R 4When being connected on the end phenol ring of polyphenylene oxide chain, can be aminoalkyl group or (dialkyl amido) alkyl, alkyl wherein contains 1 to 4 carbon atom.
R preferably 1, R 2, R 3And R 4Be selected from hydrogen and as the above-mentioned methyl that selectively replaces, and work as R 1And R 4When being connected on the terminated phenol ring, then be amino methyl or (dialkyl amido) methyl, alkyl wherein contains 1 to 4 carbon atom, for example di-n-butyl amino) methyl, and R 2And R 3Be hydrogen.
The starting compound of best general formula I is poly--2,6-dimethyl-1, and the 4-phenylate wherein is connected on the end of the chain phenol ring one or 2 methyl and is replaced by amino or dialkyl amido, and alkyl wherein contains 1 to 4 carbon atom.
Contained EPDM rubber can be selected from ethene, propylene and one or more norbornene derivatives in the composition that the present invention will prepare, as Dicyclopentadiene (DCPD) or ethylidene norbornene.
In general, multipolymer contains the norbornene derivative of 50 to 70% (weight) ethene and 05 to 12% (being preferably 4 to 9%) (weight), its number-average molecular weight (M n) be about the 40-90 kg/mol, and M w/ M nRatio be 20 to 4, be 30 to 35 preferably.
Must recognize that the EPDM rubber that is mixed should mainly be according to its aromatic monomer in the vinyl substituted that will use, more particularly, the solubleness in the vinylbenzene is selected.
The suitable example that is used for this purpose has for example Keltan K 312, Keltan514, Keltan 740 and Kelkan K 470 (trade mark).
In road piece of writing specification sheets, also only there is poly-(conjugated diolefine) block major part to be hydrogenated about the used term of segmented copolymer " alternative partial hydrogenation " even be meant hydrogenation, poly-(alkenyl aromatic) block then is not hydrogenated basically.
Must recognize that term " a spot of triblock copolymer A-B-A " is meant that the content of these multipolymers is at most 20% (weight), is preferably lower than 5% (weight).
Join by the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock A-B in the composition of the present invention's preparation and optional a small amount of triblock copolymer A-B-A and can be selected from such analog copolymer, be that its number-average molecular weight is preferably 50,000 to 800,000, the amount of the aromatic substance that wherein contained alkenyl replaces is 20 to 40% (weight), is preferably 25 to 35% (weight).
Applicable preferred Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock contains by a large amount of vinylbenzene and a small amount of conjugated diolefine and obtains a polystyrene block or unregulated polymer block and polyisoprene or poly--1, a block of 3-divinyl, the latter has 80% (mole) at least after polymerization, better have at least 95% former unsaturated link(age) in polyhutadiene or polyisoprene blocks to be hydrogenated.
The number-average molecular weight of preferred segmented copolymer is 70,000 to 500,000, and its molecular weight distribution is 10 to 15, is preferably 101 to 110.
Among the used best diblock AB, the styrene content of bonding is 25-40% (weight), wherein the number-average molecular weight of block A is 15,000 to 50,000, be preferably 15,000 to 20,000,1 of the polyhutadiene before the hydrogenation, the amount of 2-ethylenic linkage is 25 to 40%, is preferably 30 to 35% (weight).
Suitable polymer blend block A can be by following monomer preparation, for example vinylbenzene, alpha-methyl styrene, 2, the 4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, 3, the 4-dimethyl styrene ,-t-butyl styrene, to styryl phenyl, right-acetate acidic group vinylbenzene, Vinylstyrene, 1-vinyl naphthalene, 3,5-diethylbenzene ethene, 4-n-propylbenzene ethene, 2,4,6-Three methyl Benzene ethene, 4-p-methylphenyl vinylbenzene, 3,5-diphenyl benzene ethene, 3-ethyl-vinyl naphthalene or 8-phenyl-1-vinyl naphthalene or its mixture.
Vinylbenzene is the aromatic substance that preferred main alkenyl replaces, and alternative is mixed with the aromatic substance that a small amount of one or more other specific alkenyl replaces.
The suitable polymer blend B block can be by the preparation of following monomer: for example 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (isoprene), 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene, 2-methyl isophthalic acid, the 3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-divinyl or 1-phenyl-1,3-butadiene or its mixture.Isoprene and 1,3-butadiene or its mixture are preferred conjugated diolefines, as principal monomer, and 1,3-butadiene most preferably, it optionally is mixed together with a small amount of other specific conjugate diene monomer.
The example that is added into the suitable segmented copolymer in the composition of the present invention has Kraton D-1118X and Kraton G 1701X (Kraton is a trade mark), but other similar segmented copolymer also can successfully be used.
The dissolving of the conversion of the polymkeric substance that polyphenylene oxide or structure are close and rubber-like component should be carried out under the temperature of 0 to 60 ℃ (more suitable at 10 to 30 ℃).In the close polymkeric substance conversion process of polyphenylene oxide or structure, preferably use catalyzer, gross weight in the reaction mixture of the aromatic substance monomer (one or more) that comprises polyphenylene oxide and vinyl substituted, its concentration in the initial action mixture is preferably 00025 to 01% (weight), is preferably 001 to 0075% (weight).
In the gross weight of reaction mixture, the end-capping reagent of general formula I I a or II b is used in the initial action mixture, and (as the concentration in the vinylbenzene is that 005 to 05% (weight) is preferably 01 to 3% (weight).
Must recognize, use under the situation of not holding the polyphenyl ether derivative that has free hydroxyl group, should use suitably excessive end-capping reagent.
The method that prepolymerization step (c) can adopt thermal initiation or use free-radical initiator to cause is carried out, and is 110 to 150 ℃ thermal initiation method but should select temperature range for use.
In order to form the required bead of aqueous dispersion polymerization, the reaction mixture of pre-polymerization is suspended in the water.These beads can be with physics and/or chemical foaming agent (as Skellysolve A or halohydrocarbon) dipping in polymerization process or after the polymerization.If must between polymerization period, flood, then in the presence of an amount of whipping agent, pressurize and flood, can add one or more auxiliary agents at polymerization procedure (b) with (c), as filler, fiber or non-woven webs, dyestuff, stablizer or fire retardant.
Preferred embodiment according to aqueous dispersion polymerization, for the reaction mixture of aromatic monomer (one or more) that each weight part contains close polymkeric substance of the polyphenylene oxide of modification or structure and vinyl substituted, the consumption of water can be 1 to 10 part (weight), is preferably 1-2 part (weight).Used aqueous dispersions optionally contains dispersion stabilizer and one or more polymerizing catalysts.
The example of this class dispersion stabilizer comprises polyvinyl alcohol, gelatin, the sodium salt of agar, starch, glycerine, polyacrylic acid and polymethyl acrylic acid, polyoxyethylene glycol, 1: 1 multipolymer of Natvosol, carboxymethyl cellulose, methylcellulose gum, ethylene glycol, polyacrylamide and for example vinylbenzene and maleic anhydride.Based on the weight of institute's water, it is 0001 to 15% (weight) preferably that the consumption of dispersion stabilizer is generally 00001 to 3% (weight), more preferably 001 to 07% (weight).
The exemplary of polymerizing catalyst comprises decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxidation decoyl, stearoyl, peroxidation 3,5,5-trimethyl acetyl, TBPB tertiary butyl perbenzoate, tertiary butyl peracetic acid ester, the tertiary butyl are crossed pivalate, diisopropyl phenyl hydroperoxide, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane, di-t-butyl peroxide, cyclohexanone peroxide, dicumyl peroxide, α, α '-azo two (isopropyl cyanide), the tertiary butyl crosses isobutyrate and the tertiary butyl is crossed laurate.
Preferred these free-radical initiators are pyrolytic decomposition type catalyzer or with array configuration (array configuration of for example a kind of low-temperature decomposition type catalyzer and a kind of pyrolytic decomposition type catalyzer) use of two or more catalyzer.When using the form of low-temperature decomposition type catalyzer and pyrolytic decomposition type catalyst combination, beginning is carried out polymerization earlier in 85 to 95 ℃ temperature range, behind the polymerization yield rate that obtains to a certain degree, the temperature of rising reaction system is finished polyreaction basically in 110 to 130 ℃ high temperature range.
The preferably combination of catalyst system therefor comprises following combination: lauroyl peroxide and dicumyl peroxide; Lauroyl peroxide and di-t-butyl peroxide; Lauroyl peroxide and TBPB tertiary butyl perbenzoate; Lauroyl peroxide and 25-dimethyl-2,5-di-t-butyl peroxide hexane; Lauroyl peroxide and benzoyl peroxide, peroxidation 3,5,5-trimethyl acetyl and dicumyl peroxide, peroxidation 3,5,5-trimethyl acetyl and TBPB tertiary butyl perbenzoate; Peroxidation 3,5,5-trimethyl acetyl and benzoyl peroxide; Peroxidation 3,5,5-trimethyl acetyl and di-t-butyl peroxide; The tertiary butyl is crossed pivalate and di-t-butyl peroxide: the tertiary butyl is crossed pivalate and dicumyl peroxide; The tertiary butyl is crossed PIVALIC ACID CRUDE (25) and TBPB tertiary butyl perbenzoate; Peroxidation 2,4 dichloro benzene formyl and TBPB tertiary butyl perbenzoate; Peroxidation 2,4 dichloro benzene formyl and dicumyl peroxide; Peroxidation 2,4 dichloro benzene formyl and di-t-butyl peroxide, peroxidation 2,4 dichloro benzene formyl and 2,5-dimethyl-2,5-di-t-butyl peroxide hexane; Peroxidation decoyl and dicumyl peroxide; Peroxidation decoyl and di-t-butyl peroxide and benzoyl peroxide and di-t-butyl perbenzoate.
In the present invention, catalyzer uses with the amount of the aromatic substance of suitable polymeric chain alkenyl substituted.Based on the monomeric weight that is added, catalyzer suitable consumption in the present invention is 001 to 1% (weight), and best is 03 to 07%.
Another aspect of the present invention is to adopt that for example injection moulding mold pressing or extrusion process etc. are made moulded products with swelling property or non-expansibility bead shape polymer composition that preceding method obtained.
Described polymer composition comprises:
(a) the close polymkeric substance of at least a polyphenylene oxide or structure, wherein original free hydroxyl group is by transforming by the end-capping reagent end-blocking, and its content is 5 to 30% (weight), is preferably 10 to 25% (weight);
(b) poly-(aromatic substance that alkenyl replaces);
(c) at least a EPDM rubber that obtains by ethene, propylene and norbornene derivative monomer, its proportion is 085 to 095, mooney viscosity (125 ℃ of ML (1+4)) is 30 to 80, ethylene content is 50 to 80% (weight), the content of this rubber is 5 to 20% (weight), be preferably 7 to 15% (weight amounts)
D) a kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock AB, alternative is mixed with a small amount of triblock copolymer ABA, wherein A is preferably polystyrene for poly-(aromatic substance that alkenyl replaces) block, and B is the polymerized conjugated diene block of selective hydration, be preferably polyhutadiene or poly-different diene, the number-average molecular weight of segmented copolymer is 10,000 to 1000,000, content is 1 to 5% (weight), is preferably 2 to 4% (weight).
These compositions are characterised in that to have very tempting mechanical property and thermal characteristics, especially have the otch Ako that excellent impact can be for example measures by DIN 53453 (Izo norm179) (℃) be 47 to 60K J/m 2
As if it is believed that these characteristics, especially excellent impact are that the characteristic continuous microstructure of the blend polymer that obtains with preceding method is caused, these characteristics still can keep the back for several times repeating to process common blend.
Must recognize, the surprising tempting performance of the microstructure of this specific blend polymer and these blends of therefore causing only the EPDM rubber content, in prepolymerization step the content three of vinyl monomer transformation efficiency and polyphenylene oxide variation spoke degree all under quite little situation three's combination could obtain, as if thereby the three must all have a value in specialized range separately.
Described conventional continuous chemical blending structure and discontinuous, both comparative results of dispersive mechanical blending structure that adopt that conventional combination technique (promptly using the fusing kneader, as single screw rod or twin-screw extruder etc.) obtains can from the electron micrograph (Fig. 1 and Fig. 2) of composition that the present invention obtains and with the electron micrograph (Fig. 3) of existing machinery composition that blending technology obtains find out.
The following example will further specify the present invention, but the invention is not restricted to these specific embodiments.
Embodiment 1
With 15 gram number-average molecular weight (M n) be 20,000 to 30,000 poly--2,6-dimethyl-1,4-phenylate (for example the PPE type 800 and 808 of general electric plastics, the limiting viscosity in chloroform in 25 ℃ under (IV) is 046 and 040) at room temperature is dissolved in 72 and restrains in the vinylbenzene, lasts about 1 hour.In the gross weight of reaction mixture, then add 01% (weight) diacetyl oxide and 001 (weight) N respectively, N-dimethyl-4-aminopyridine (DMAP).After at room temperature stirring 1 hour, in the small sample that is settled out reaction mixture under the room temperature in methyl alcohol, and with infrared absorption spectrum it is measured, the result is at 1765cm -1Place's display characteristic absorbs maximum value, but does not see the characteristic absorption maximum value relevant with the existence of free hydroxy-terminal.
Add 10 grams then in the reaction mixture and contain 66% (weight) vinyl monomer and monomeric EPDM rubber (the Keltan K 740 of 1% ethylidene norbornene, Keltan is a trade mark) and 3 gram polystyrene-hydrogenated polyisoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks (Kraton G 1701X, Kraton is a trade mark).
Behind these rubber of dissolving, temperature is risen to about 70 ℃, stir down and carry out prepolymerization, so that the polymerization degree reaches 15% at 130 ℃.Adding 150 grams in the reaction mixture, to contain 02% (weight) Natrosol 250G (Natrosol is a trade mark) and temperature be 70 ℃ water.
In the presence of dibenzoyl peroxide (DBPO), the suspension that is obtained was heated to 93 ℃ and radical polymerization then 5 hours, and then under TBPB tertiary butyl perbenzoate (TBPB), reacted 3 hours in 120 ℃ of continuation.
The T that the rule spherical-shaped beads is arranged that is obtained gValue is about 110 ℃, and the resistance to impact shock Ako (0 ℃, otch) that records by DIN53453 (Izo norm 179) is 49K J/m 2
Embodiment 2
Use diacetyl oxide and DMAP, prepare end capped PPE by the method identical with embodiment 1, add in the reaction mixture 10 grams contain 55% (weight) ethene and 4% polymerization ethylidene norbornene (keltan k 312, Keltan is a trade mark) EPDM rubber and 3 gram Kraton D-1118X (Kraton is a trade mark) (polystyrene-hydrogenated butadiene polymer Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the weight ratio of phenylethylene/butadiene is about 30: 70, the number-average molecular weight of styrene block is 15,000 to 20,000).
Carry out prepolymerization earlier by the method identical, carry out suspension polymerization again, the T that the rule bead is arranged that is obtained with embodiment 1 gValue is about 110 ℃, and resistance to impact shock (otch) Ako (0 ℃) that records by DIN 53453 (Izonorm 179) is 48KJ/m 2
Embodiment 3
At room temperature be that 20,000 to 30,000 PPE is dissolved in the 72 gram vinylbenzene, last about 1 hour 150 gram number-average molecular weights.With the total weight of reaction mixture, then add the maleic anhydride and the sodium hydride of 01% (weight) respectively.
After at room temperature stirring 1 hour, at room temperature be settled out the spiece sample in methyl alcohol, and with infrared absorption spectrum it measured, the result is at 3500-2700cm -1, 1710cm -1And 1725cm -1The maximum value that place's display characteristic absorbs.
Then toward reaction mixture add 10g contain 55% (weight) ethene and 45% (weight) polymerization the EPDM rubber and the 3g Kraton D-1118X (Kraton is a trade mark) of Dicyclopentadiene (DCPD) (Keltan K 740, Keltan are trade marks).
Carry out polymerization by the method identical with embodiment, the Tg value that the rule spherical-shaped beads is arranged that is obtained is 111 ℃, and the resistance to impact shock (otch) that records by DIN 53453 (Izo norm 179) is 50KJ/m 2
Embodiment 4
At room temperature with 10g PPE (general electric plastics, 800 types, IV ± I, V ,=046 (OHO1 3, 25 ℃)) be dissolved in the 80g vinylbenzene, last about 1 hour.
Then add the mixture of 015% (weight) diacetyl oxide and 0017% (weight) DMAP (Dimethylamino pyridine) respectively, above-mentioned weight percent is a benchmark with the gross weight of reaction mixture.
Behind the PPE end-blocking, temperature is risen to 70 ℃, the regulation of pressing embodiment 1 then adds 5g EPDM in reaction mixture.Carry out polymerization by embodiment 1 described method, difference is that continuing prepolymerization at 130 ℃ carries out suspension polymerization at 90 ℃ after the polymerization degree is 10%, 5 hour, adds 7% pentane toward mixture, and causing reactor pressure is 7-8bar.
After 1 hour, proceed reaction 90 ℃ of reactions with TBPB.
What obtain to contain pentane thus has a rule spherical-shaped beads.Can produce suitable foam by this blend.
Embodiment 5
At room temperature be that 20,000 to 30,000 PPE (general electric plastics, 800 types) is dissolved in the 100g vinylbenzene, last about 1 hour the 10g number-average molecular weight.
Then add toluene sulfonyl chloride, triethylamine and DMAP, add-on is so that its concentration is respectively 02% and 005% (weight) (in the gross weight of reaction system).After at room temperature stirring 1 hour, heated mixt adds 10gEPDM rubber (Keltan K 740, Keltan are trade marks) until 70 ℃.Heated solution to 130 ℃ then, and carry out pre-polymerization and transform up to 10% polystyrene, add 130 gram temperature toward the entire reaction mixture and be 70 ℃ and contain in the water of 02%Natrosol250G (Natrosol is a trade mark).
Under embodiment 1 described standard reaction condition, carry out polymerization, the resulting T that the rule spherical-shaped beads is arranged gValue is 110 ℃, and (otch) resistance to impact shock that records by DIN 53453 is 50KJ/m 2

Claims (16)

1. contain the polymer composition of poly-(aromatic substance that alkenyl replaces), said composition obtains with following method:
(a) in the aromatic monomer that at least a alkenyl replaces, polyphenylene oxide shown in the following formula or the close polymkeric substance of structure are transformed with acyl halide, acid anhydrides or ketenes,
Figure F901044989C0000021
R in the formula 1And R 4Can respectively be chlorine, halogen, phenyl, alkenyl, alkadienyl, aryloxy or R 1And R 4Can respectively be alkyl and alkoxyl group; these two kinds of groups can respectively contain 12 or carbon atom still less and optionally each by halogen, cyano group, hydroxyl, phenyl or amino the replacement; the alkyl or the alkoxyl group that are connected on the terminated phenol ring then can be replaced by amino, dialkyl amido or two (alkyloyl) amido; alkyl in these substituting groups respectively contains 4 or carbon atom still less, R in the formula 2And R 3Can respectively be hydrogen, halogen, phenyl, alkenyl, alkadienyl, aryloxy, perhaps R 2And R 3As R 1And R 4Defined can respectively be uncle or secondary alkyl or uncle or secondary alkoxyl group like that, and these groups are optionally replaced R in the formula by halogen cyano group, hydroxyl, phenyl 1, R 2, R 3And R 4Can respectively be similar and different group in a multiple unit, n be at least 50 integer, is preferably 100 to 500, and in the gross weight of final composition, the consumption of the polymkeric substance that polyphenylene oxide or structure are close is 5 to 30% (weight);
(b) at least a ethylene-propylene-diene monomers (EPDM) rubber of dissolving 5 to 20% (weight) and the alternative partially hydrogenated Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock A-B of 1 to 5% (weight), optionally be mixed with a small amount of triblock copolymer A-B-A in this Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, above-mentioned weight hundred scores are all in the gross weight of final composition; The proportion of above-mentioned rubber is 085 to 095, and mooney viscosity (125 ℃ of ML (1+4)) is 30 to 80, and therein ethylene content is 50 to 70% (weight); In above-mentioned segmented copolymer, A is poly-(alkenyl aromatic compounds) block, and B is alternative partially hydrogenated polymerized conjugated diene block, and the number-average molecular weight of segmented copolymer is 10,000 to 1,000,000, and second-order transition temperature is-20 ℃ or lower;
(c) mixture that prepolymerization obtained is 5 to 20% until the polymerization degree;
(d) polymeric thing piece is suspended in the water medium;
(e) adopt thermal initiation or carry out polymerization with the mode that at least a free-radical initiator causes, this polyreaction is optionally carried out in whipping agent.
2. the described polymer composition of claim 1 is characterized in that obtaining in the method for said composition step (a) and carries out in the mixture that mainly contains styrene monomer.
3. the described polymer composition of claim 1, its feature in obtaining the method for said composition step (a) in the presence of a kind of catalyzer, also optionally in the presence of neutralizing agent, adopt acyl chlorides or non-annularity acid anhydrides to carry out as end-capping reagent, described end-capping reagent is selected from the compound shown in the following general formula
Figure F901044989C0000031
X in the formula 1For chlorine or contain the alkyl of the individual carbon atom in 1 to 4 (best 1 to 2), this alkyl is optionally replaced by halogen, X in the formula 2Be halogen, R 5Full R 6Can respectively be alkyl, alkenyl, aryl (preferably phenyl) or aralkyl (preferably aromatic yl elementary alkyl), these groups contain 1 to 12 carbon atom and alternative by hydroxyl, halogen (preferably bromine), contain the alkyl of 1 to 4 carbon atom or the carboxyl substituted of free or esterification, above-mentioned catalyzer has following general formula:
Figure F901044989C0000041
In the formula, R 9And R 10Be generally non-electron-withdrawing group, as contain the alkyl of 1 to 4 carbon atom, this alkyl is alternative by phenyl replacement at the most, R 7And R 8Be hydrogen, halogen or low alkyl group, and at same intramolecular R 9And R 10Can be similar and different.
4. the described polymer composition of claim 3 is characterized in that obtaining in the method for said composition step (a) and adopts and react to the 2-bromomethylphenyl sulfuryl bromide or to 2-bromomethylphenyl SULPHURYL CHLORIDE, diacetyl oxide, benzoyl oxide or bromoacetic acid acid anhydride.
5. the described polymer composition of claim 4 is characterized in that obtaining that step (a) adopts diacetyl oxide to react in the method for said composition.
6. each described polymer composition among the claim 1-5.It is characterized in that obtaining that step (a) adopts in the method for said composition, N, N-dimethyl-4-aminopyridine reacts as catalyzer.
7. each described polymer composition among the claim 1-4 is characterized in that obtaining that step (a) adopts acyl halide and additional acid neutralizing agent to react in the method for said composition.
8. the described polymer composition of claim 7 is characterized in that obtaining that step (a) adopts 2-bromomethylphenyl alkylsulfonyl bromine in the method for said composition, N, and N-dimethyl-4-aminopyridine and triethylamine or three n-propyl amine react.
9. the described polymer composition of claim 1 is characterized in that obtaining in the method for said composition step (a) and reacts with being selected from the end-capping reagent shown in the following formula in the presence of non-nucleophilic base,
Figure F901044989C0000051
Y is the divalent group of following formula in the formula;
Figure F901044989C0000052
M is 2 to 8 integer in the formula, is preferably 2 to 4 integer, R 11And R 12Can be respectively for containing alkyl, phenyl or the aralkyl (being preferably phenmethyl) of 1 to 4 carbon atom, perhaps R 11And R 12Carbon atom with carbon-to-carbon double bond forms cycloalkenyl group, cycloalkadienyl or aryl.
10. the described method of claim 9 is characterized in that obtaining that step (a) adopts maleic anhydride and sodium hydride to react in the method for said composition.
11. each described polymer composition in the claim 1 to 10 is characterized in that said composition comprises the polyphenylene oxide of general formula I, R in the formula 1And R 4Be methyl, optionally replaced R in the time of on being connected terminal phenol ring by amino or dialkyl amido 2And R 3Be hydrogen.
12. each described polymer composition in the claim 1 to 11, it is characterized in that in the step (a) of the method that obtains said composition the close polymkeric substance of polyphenylene oxide or structure adds in the consumption (with the gross weight of whole composition) of 10 to 25% (weight).
13. each described polymer composition in the claim 1 to 12 is characterized in that pre-polymerization is right to be 8 to 15% in the step (c) of the method that obtains said composition.
14. each described polymer composition in the claim 1 to 13, it is characterized in that in the step (b) of the method that obtains said composition, using the EPDM multipolymer, this multipolymer contains the ethene of 50-70% (weight) and the norbornene derivative of 05 to 12% (weight), and the number-average molecular weight of multipolymer is 40 to 90kg/mole.And M w/ M nBeing 20 to 40, is 30 to 35 preferably.
15. each described polymer composition in the claim 1 to 14, it is characterized in that in the step (b) of the method that obtains said composition, using diblock AB multipolymer, its number-average molecular weight is 50,000 to 800,000, wherein the content of the aromatic substance of alkenyl replacement is 20 to 40%, is preferably 25 to 35% (weight).
The method of the polymer composition that 16. preparation contains poly-(aromatic substance that alkenyl replaces), this method comprises:
(a) in the aromatic monomer that at least a alkenyl replaces, polyphenylene oxide shown in the following formula or the close polymkeric substance of structure are transformed with acyl halide, acid anhydrides or ketenes,
Figure F901044989C0000061
R in the formula 1And R 4Can respectively be hydrogen, halogen, phenyl, alkenyl, alkadienyl, aryloxy, perhaps R 1And R 4Can respectively be alkyl and alkoxyl group; these two kinds of groups can respectively contain 12 or carbon atom still less and optionally each by halogen, cyano group, hydroxyl, phenyl or amino the replacement; the alkyl or the alkoxyl group that are connected on the terminated phenol ring then can be replaced by amino, dialkyl amido or two (alkyloyl) amido; alkyl in these substituting groups respectively contains 4 or carbon atom still less, R in the formula 2And R 3Can respectively be hydrogen, halogen, phenyl, alkenyl, alkadienyl, aryloxy, perhaps R 2And R 3As R 1And R 4Defined can respectively be uncle or secondary alkyl or uncle or secondary alkoxyl group like that, and these groups are optionally replaced by halogen, cyano group, hydroxyl, phenyl.R in the formula 1, R 2, R 3And R 4Can respectively be similar and different group in a multiple unit, n be an integer, and its value is at least 50, is preferably 100 to 500, and in the gross weight of final composition, the consumption of the polymkeric substance that polyphenylene oxide or structure are close is 5 to 35% (weight);
(b) at least a ethylene-propylene-diene monomers (EPDM) rubber of dissolving 5 to 20% (weight) and the alternative partially hydrogenated Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock A-B of 1 to 5% (weight), optionally be mixed with a small amount of triblock copolymer A-B-A in this Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, above-mentioned weight percent is all in the gross weight of final composition; The proportion of above-mentioned rubber is 085 to 095, and mooney viscosity (125 ℃ of ML (1+4)) is 30 to 80, and therein ethylene content is 50 to 70% (weight); In above-mentioned segmented copolymer, A is poly-(alkenyl aromatic compounds) block, and B is alternative partially hydrogenated polymerized conjugated diene block, and the number-average molecular weight of segmented copolymer is 10,000 to 1,000,000, and second-order transition temperature is-20 ℃ or lower;
(c) mixture of prepolymerization acquisition is 5 to 20% until the polymerization degree;
(d) the thing piece that prepolymerization is got is suspended in the water medium;
(e) adopt thermal initiation or carry out polymerization with the mode that at least a free-radical initiator causes, this polyreaction is optionally carried out in whipping agent.
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